JP2003119368A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant aromatic polycarbonate resin composition capable of exhibiting high flame retardancy, even though it contains a flammable styrene-based resin, by using an organopolysiloxane having a specific structure and one or more specific inorganic metal salts as flame retardants. SOLUTION: This flame-retardant polycarbonate resin composition comprises 100 pts.wt. of (A) a resin component comprising 50-95 wt.% of the aromatic polycarbonate and 50-5 wt.% of the styrene-based resin, 0.1-30 pts.wt. of (B) the organopolysiloxane, and 0.0005-5 pts.wt. of (C) an inorganic alkali metal salt and/or an inorganic alkaline earth metal salt, wherein the organopolysiloxane (B) contains monofunctional siloxane units, bifunctional siloxane units, trifunctional siloxane units, and tetrafunctional siloxane units in amounts of 0-70 mol%, 0-100 mol%, 0-100 mol%, and 0-63 mol%, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polycarbonate resin composition, and more specifically, it is flame-retarded with an organopolysiloxane having a specific structure and a specific inorganic alkali metal salt and / or inorganic alkaline earth metal salt. Aromatic polycarbonate resin composition.

[0002]

2. Description of the Related Art Aromatic polycarbonate is known as an engineering plastic excellent in impact resistance, heat resistance, transparency and the like, and particularly, OA equipment, home electric appliances,
Widely used in the field of information and communication equipment. In addition, in these fields, in order to cope with complicated parts shapes and thinner walls, it is also possible to improve the melt flowability of aromatic polycarbonate by increasing the injection moldability by blending styrene resin with aromatic polycarbonate. Many are done. As the styrene resin used here, a rubber-modified styrene resin is generally used in consideration of physical properties such as impact resistance.

On the other hand, in such electric / electronic fields, materials used are required to have high flame retardancy in order to enhance the safety of products. Aromatic polycarbonate has a limiting oxygen index of 26 to 27, which is an index of flame retardancy.
And is known to be a self-extinguishing resin.
This is because the main chain of the aromatic polycarbonate molecule is mainly composed of aromatic rings, so that not only thermal decomposition reaction but also rearrangement reaction, cyclization reaction, cross-linking reaction, etc. occur during combustion.
This is considered to be for easily forming a carbonized layer (char) having extremely high flame retardancy.

On the other hand, a styrene resin is a flammable resin having a limiting oxygen index of only 18, and it is extremely difficult to prevent its combustion. It is considered that this is because the styrene-based resin is depolymerized by combustion, and the resulting monomer component serves as fuel to continue combustion and accelerate it. Therefore, in the resin mixture of the aromatic polycarbonate and the styrene resin, it becomes more difficult to achieve high flame retardancy as the blending amount of the styrene resin is increased in order to improve the moldability.

As a technique for imparting flame retardancy to a resin, a method of blending a flame retardant aid such as a halogen-based flame retardant or antimony oxide has been conventionally used. However, due to the recent growing interest in environmental problems, conversion to flame retardants with higher safety is being considered.

When imparting flame retardancy to an aromatic polycarbonate or a resin mixture of an aromatic polycarbonate and a styrene resin, a method of using a phosphate ester compound as a flame retardant is generally used. However, phosphoric acid ester compounds are susceptible to hydrolysis and thermal decomposition, and there is a problem that the generated phosphoric acid lowers the molecular weight of the polycarbonate and reduces the mechanical properties of the resin, making it a safer and more reliable flame retardant. The demand for is increasing.

Organopolysiloxane is one of the non-halogen flame retardants that has been studied for a long time because of its high safety. Generally, the organopolysiloxane is

The following equation (5):

[Chemical 5] A monofunctional unit (M unit) represented by

The following equation (6):

[Chemical 6] A difunctional unit (D unit) represented by

The following equation (7):

[Chemical 7] (R in formulas (5) to (7) are each independently a monovalent organic group), and a trifunctional unit (T unit), and

The following equation (8):

[Chemical 8] Is a polymer containing a plurality of at least one repeating unit selected from the group consisting of tetrafunctional units (Q units) represented by:

For example, JP-A-10-139964 (corresponding to EP 0 829 521) and JP-A-11-140294 (German Patent No. 1985).
No. 0453) discloses a technique in which a branched organopolysiloxane having D units and T units as main constituent units and optionally Q units is used as a flame retardant for aromatic polycarbonate.

However, since the effect of improving the flame retardancy when the organopolysiloxane is used alone is insufficient, many techniques of using other flame retardants in addition to the organopolysiloxane have been studied.

As the flame retardant used in combination, an organic metal salt represented by an aromatic sulfonic acid metal salt or a perfluoroalkane sulfonic acid metal salt is generally used, and in addition, dripping of combustion particles generated at the time of combustion (drip) In order to prevent this, a fluorine-containing olefin resin such as polytetrafluoroethylene is often added.

For example, Japanese Patent Laid-Open No. 6-306265,
JP-A-6-336547 (U.S. Pat. No. 5,44)
(Corresponding to JP-A-9,710) and the like, a method of adding an organopolysiloxane mainly composed of D units and an alkali or alkaline earth metal salt of perfluoroalkanesulfonic acid to an aromatic polycarbonate is disclosed.

JP-A-11-217494 (EP
(Corresponding to Japanese Patent No. 1035169), Japanese Patent Laid-Open No. 2000-3
Publication No. 02961 (International application publication WO2000 / 649
No. 76), JP-A-2000-226527, JP-A-2001-200150, etc., organopolysiloxanes having various branched structures mainly composed of D units, T units and Q units are described as organic compounds. A technique is disclosed in which a polycarbonate resin is used in combination with a sulfonic acid metal salt and a fluoropolymer.

Further, Japanese Patent Laid-Open Nos. 8-176425 and 11-222559 (US Pat. No. 6,18)
No. 4,312), JP-A-11-263903.
Japanese Patent Laid-Open No. 2001-26704 also discloses a technique of using an organopolysiloxane having various structures in combination with an organic metal salt as a flame retardant for an aromatic polycarbonate. In the publications mentioned above, the resins used are all aromatic polycarbonates, and no specific examples are disclosed regarding the flame retardancy-improving effect on the resin mixture consisting of the aromatic polycarbonate and the styrene resin. . It is considered that this is probably because the flame retardancy improving effect is still insufficient due to the easiness of combustion of the styrene resin as described above.

Examples of the technique of using a combination of an organopolysiloxane and an organic sulfonate as a flame retardant in a resin mixture composed of an aromatic polycarbonate and a styrene resin include, for example, International Application Publication WO99 / 40.
No. 158, Japanese Patent Laid-Open No. 2000-159996.
JP-A 2000-256566 and 2000
-345045, International Application Publication WO2000 / 4
6299 and Japanese Patent Laid-Open No. 2001-72867.

However, in the examples of these publications, a large amount of organic sulfonic acid metal salt is used in order to achieve high flame retardancy while using a styrene resin together.

Metal salts of organic sulfonic acids represented by perfluoroalkane sulfonic acids and aromatic sulfonic acids, particularly alkali metal salts and alkaline earth metal salts, are effective for flame retarding aromatic polycarbonates even if added in small amounts. Therefore, it has been used for a long time (for example, Japanese Patent Publication No. 47-404).
45, Japanese Patent Publication No. 57-43099, Japanese Patent Publication No. 5
7-43100).

Regarding the mechanism of action of the sulfonic acid metal salt,
For example, G.I. Journal by Montaud et al.
of Polymer Science, Poly
mer Chemistry, Vol. 26, No. 2113
The paper on page (1988) states that the organic sulfonate is to accelerate the thermal decomposition of the polycarbonate to promote the formation of a carbonized layer.

Therefore, when a large amount of the organic sulfonate is used with respect to the aromatic polycarbonate, the thermal stability of the aromatic polycarbonate is lowered, and the molecular weight is lowered during the kneading / molding work, and mechanical properties are likely to be impaired.

Further, as will be described later, according to the study by the present inventors, it is attempted to reduce the amount of the organic sulfonate used in the resin mixture of the aromatic polycarbonate and the styrene resin in order to avoid deterioration of mechanical properties. However, it has been found that not only the flame retardancy improving effect is lowered, but also the combustion is accelerated.

On the other hand, as a technique of using a salt other than an organic sulfonate as a flame retardant for an aromatic polycarbonate,
For example, a method using an alkali metal halide (JP-A-49-88944, JP-A-49-107049).
JP-A-49-125464, JP-A-50
-83448, etc.); Method using alkali metal or alkaline earth metal salt of sulfurous acid, thiosulfuric acid, dithionous acid, pyrosulfurous acid (JP-A-52-17557, JP-A-52-17558). JP-A-48-43751, JP-A-53-888. A method using a fluorine-containing complex salt such as sodium hexafluoroaluminate and potassium hexafluorosilicate.
56, JP-A-53-96055, JP-A-5
(See JP-A-5-151057, etc.) and the like.

However, a technique of using a salt other than these organic sulfonates together with an organopolysiloxane as a flame retardant for a resin mixture comprising an aromatic polycarbonate and a styrene resin has not been known so far.

[0026]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has an excellent flame retardance while using a highly safe organopolysiloxane even if the resin component contains a highly flammable styrene resin. An object is to provide an aromatic polycarbonate resin composition exhibiting properties.

[0027]

In order to achieve the object of the present invention, the inventors of the present invention have conducted extensive studies focusing on a salt used in combination with an organopolysiloxane. As a result, surprisingly, when an inorganic alkali metal salt and / or an inorganic alkaline earth metal salt is used in combination with an organopolysiloxane, an aromatic polycarbonate and styrene can be added with an extremely small amount compared with the case where an organic sulfonate is used. The inventors have found that flame retardancy can be imparted to a resin mixture composed of a series resin, and have completed the present invention.

That is, according to the present invention, 50 to 95% by weight of the aromatic polycarbonate and 50 of the styrene resin.
˜5% by weight of the resin component (A) 100 parts by weight, the organopolysiloxane (B) 0.1 to 30 parts by weight, and the inorganic alkali metal salt and / or the inorganic alkaline earth metal salt (C) 0.0005 to A flame-retardant polycarbonate resin composition comprising 5 parts by weight, wherein the organopolysiloxane (B) is

The following formula (1):

[Chemical 9]

(In the formula, each R independently has 1 to 20 carbon atoms.
Monovalent hydrocarbon group, monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, mercaptoalkyl group having 1 to 20 carbon atoms, cyanoalkyl group having 2 to 20 carbon atoms, and 2 to 2 carbon atoms
0 acyloxyalkyl group, C1-20 aminoalkyl group, C6-20 aminoaryl group, C1-20 hydroxyalkyl group and C4-2
1 selected from the group consisting of 0 glycidoxyalkyl groups
It is a valent organic group. ) A monofunctional siloxane unit (M unit) represented by:

The following equation (2):

[Chemical 10] (In the formula, R is the same as that defined in the above formula (1).) A difunctional repeating siloxane unit (D
unit);

The following equation (3):

[Chemical 11] (In the formula, R is the same as that defined in the above formula (1).) The trifunctional repeating siloxane unit (T
unit);

The following formula (4):

[Chemical 12] A tetrafunctional repeating siloxane unit (Q unit) represented by
Including,

The M in the organopolysiloxane (B)
The content of the M unit, the D unit, the T unit, and the Q unit in the organopolysiloxane (B) is based on the total molar amount of the unit, the D unit, the T unit, and the Q unit. , Each 0
~ 70 mol%, 0-100 mol%, 0-100 mol%,
There is provided a composition characterized in that it is 0-63 mol%.

The present invention will be described in detail below. The resin component (A) used in the present invention comprises a resin mixture of an aromatic polycarbonate and a styrene resin.

In the present invention, the aromatic polycarbonate used as the resin component (A) has the following formula (9).

[Chemical 13]

(Wherein Ar represents a divalent phenolic compound residue), which has a main chain consisting of repeating units, and is used for the reaction between the divalent phenolic compound and the carbonate precursor, It is produced by polymerizing a carbonate prepolymer.

Specifically, an interfacial polymerization method (phosgene method) in which a dihydric phenol compound and phosgene are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent, 2
It is possible to use those produced by a method such as a transesterification method (melting method) of reacting a dihydric carbonate with a dihydric phenol compound, a solid phase polymerization method using a crystallized carbonate prepolymer, or the like.

Examples of dihydric phenol compounds include 2,2
-Bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxy-3,5-
Dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 4,4′-dihydroxydiphenyl, 4,
4'-dihydroxy-3,3 ', 5,5'-tetramethyldiphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4
-Hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl)
Ketone, bis (4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenyl) sulfone, bis (4-
Hydroxyphenyl) sulfoxide, hydroquinone,
Resorcinol, catechol and the like, especially 2,
2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. These dihydric phenol compounds may be used alone or in combination of two or more.

In order to control the molecular weight of the aromatic polycarbonate, the polymerization reaction for producing the aromatic polycarbonate is carried out by using phenol, p-methylphenol, m-methylphenol, p-propylphenol, m-propylphenol, p-. It may be carried out in the presence of a monohydric phenol compound such as t-butylphenol, pt-octylphenol and p-cumylphenol.

The aromatic polycarbonate used in the present invention may have a branched structure. The aromatic polycarbonate having a branched structure can be produced by the same method as the above-mentioned method for producing an aromatic polycarbonate, except that the polymerization reaction is carried out in the presence of a branching agent.

Examples of branching agents are 1,1,1-tris (4-hydroxyphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene, α, α ',
α ″,-tris (4-hydroxyphenyl) -1,3
5-triisopropylbenzene, phloroglucin, 4,
6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, isatin bisphenol [3,3-bis (4-hydroxyphenyl) oxindole] and the like can be mentioned.

The aromatic polycarbonate used in the present invention preferably has substantially no halogen in its structure. From the viewpoint of mechanical strength and moldability, the viscosity average molecular weight is preferably 10,000 to 100,000, and particularly preferably 14,000 to 40,000. The viscosity average molecular weight of the aromatic polycarbonate can be determined by converting the solution viscosity (using methylene chloride as a solvent).

In the present invention, the styrene-based resin used as the resin component (A) is a rubber-modified styrene-based resin and / or a rubber-unmodified styrene-based resin. Particularly, the rubber-modified styrene-based resin alone or the rubber-modified styrene-based resin is used. Mixtures of rubber-unmodified styrenic resins are preferred.

The rubber-modified styrenic resin means a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a styrene-based resin. Styrene and α-methylstyrene are present in the presence of the rubber-like polymer. , An aromatic vinyl monomer such as p-methylstyrene, or, if desired, a monomer mixture obtained by adding another monomer copolymerizable therewith to the above aromatic vinyl monomer. It can be obtained by graft (co) polymerization by known polymerization methods such as bulk polymerization, emulsion polymerization and suspension polymerization.

Examples of the rubber-like polymer used here include polybutadiene, poly (styrene-butadiene),
Diene rubber such as poly (acrylonitrile-butadiene), isoprene rubber, chloroprene rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene-
Diene monomer terpolymer (EPDM), ethylene-
Examples thereof include an octene copolymer rubber, a composite rubber containing an organopolysiloxane component and an alkyl (meth) acrylate component (silicon / acrylic composite rubber).

Examples of other monomers copolymerizable with the above aromatic vinyl monomer include unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, acrylic acid,
Examples thereof include vinyl monomers such as methacrylic acid, alkyl acrylate, alkyl methacrylate, maleic anhydride, and N-substituted maleimide.

The content of the rubber-like polymer in the rubber-modified styrene resin is in the range of 5 to 80% by weight, preferably 10 to 60% by weight. If the content of the rubber-like polymer is less than 5% by weight, the impact resistance of the resin composition will be insufficient, and if it exceeds 80% by weight, the rigidity and thermal stability will decrease, and the melt fluidity will decrease. Problems such as gel generation and coloring occur. The average particle size of the rubber-like polymer in the rubber-modified styrene-based resin is preferably 0.1 to 2.0 μm, more preferably 0.1 to 1.0 μm, still more preferably 0.2 to 0.6.
μm. When it is less than 0.1 μm, the impact resistance of the resin composition is insufficiently improved, and when it exceeds 2.0 μm, the fluidity of the resin composition and the appearance of the molded product are deteriorated.

Preferred examples of the rubber-modified styrenic resin include high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile. -Ethylene propylene rubber-styrene copolymer (AES resin), methyl methacrylate-butadiene-styrene copolymer (MBS
Resin) and the like. A composite rubber-based graft copolymer obtained by grafting the above vinyl monomer onto a silicone / acrylic composite rubber can also be used as the rubber-modified styrene-based resin.

On the other hand, the rubber-unmodified styrenic resin is obtained by the same method as the rubber-modified styrenic resin, except that the rubber-like polymer is not used. That is, aromatic vinyl monomers such as styrene, α-methylstyrene and p-methylstyrene, and unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid and acrylic acid, if desired. Alkyl,
It is a polymer obtained by (co) polymerizing vinyl monomers such as alkyl methacrylate, maleic anhydride, and N-substituted maleimide. Examples of rubber-unmodified styrenic resins include
Examples thereof include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), butyl acrylate-acrylonitrile-styrene copolymer (BAAS resin), and the like.

The reduced viscosity η _{sp of the} matrix resin portion, which is a measure of the molecular weight of the styrene resin used in the present invention,
/ C (0.005 g / cm ³ , at a temperature of 30 ° C., measured with a toluene solution when the matrix resin is polystyrene and with a methyl ethyl ketone solution when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer). , 30
Is preferably in the range of ~80cm ³ / g, more and more preferably in the range of 40~60cm ³ / g. Examples of means for satisfying the above requirements regarding the reduced viscosity η _sp / c of the styrene resin include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent.

In the resin component (A) of the present invention, the compounding ratio of the aromatic polycarbonate and the styrene resin is 50 to 95% by weight of the aromatic polycarbonate, preferably 65 to 65%.
95% by weight, more preferably 75 to 90% by weight,
The styrene resin is 50 to 5% by weight, preferably 35 to 5% by weight, and more preferably 25 to 10% by weight. If the aromatic polycarbonate is less than 50% by weight, the heat resistance, strength and flame retardancy are not sufficient, and the styrene resin is 5% by weight.
If it is less than the above range, the effect of improving the moldability is insufficient.

The organopolysiloxane used as the component (B) of the present invention is one of the components that plays an important role in imparting flame retardancy to the resin component (A).

The organopolysiloxane (B) used in the present invention is a monofunctional siloxane unit (hereinafter referred to as "M").
Unit)), difunctional repeating siloxane units (hereinafter referred to as “D units”), trifunctional repeating siloxane units (hereinafter referred to as “T units”), and tetrafunctional repeating siloxane units (hereinafter referred to as “Q units”). ").

The content of each unit in the organopolysiloxane (B) is based on the total molar amount of M unit, D unit, T unit and Q unit in the organopolysiloxane (B).
M unit is 0 to 70 mol%, D unit is 0 to 100 mol%,
The T unit is 0 to 100 mol% and the Q unit is 0 to 63 mol%.

The M unit is a unit constituting the terminal group, and when the content thereof exceeds 70 mol%, the molecular weight of the organopolysiloxane (B) becomes low, and as a result, as will be described later, the organopolysiloxane (B Is too high in volatility or has too high compatibility with the resin component (A) to plasticize the resin component (A). As a result, the flame retardancy of the resin composition decreases, which is not preferable.

The Q unit is a unit forming a crosslinked structure, and when the content thereof exceeds 63 mol%, gelation occurs during the production of the organopolysiloxane (B) or the organopolysiloxane (B) is Since the molecular weight becomes too high, the dispersibility in the resin component (A) decreases, and the flame retardancy improving effect decreases, which is not preferable.

The content of D units and T units in the organopolysiloxane (B) is not limited and can be arbitrarily used.

The more preferable content of each unit in the organopolysiloxane (B) is M unit based on the total molar amount of M unit, D unit, T unit and Q unit in the organopolysiloxane (B). Is 0 to 50 mol%, D unit is 0 to
100 mol%, T unit is 0 to 90 mol%, Q is 0 unit
It is 60 mol%.

The organic groups R in the M unit, D unit and T unit constituting the organopolysiloxane (B) used in the present invention are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a carbon group. C1-C20 monovalent halogenated hydrocarbon group, C1-C20 mercaptoalkyl group, C2-C20 cyanoalkyl group, C2-C20 acyloxyalkyl group, C1-C20 Aminoalkyl group, C6-20 aminoaryl group, C1-2
It is a monovalent organic group selected from the group consisting of a hydroxyalkyl group having 0 and a glycidoxyalkyl group having 4 to 20 carbon atoms.

Examples of the hydrocarbon group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-butyl group.
Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group Alkyl group such as group; alkenyl group such as vinyl group, allyl group, 5-hexenyl group, 4-vinylcyclohexyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, phenyl group Aryl groups such as biphenyl group, naphthyl group, tolyl group, xylyl group and ethylphenyl group; benzyl group,
Examples thereof include aralkyl groups such as α-phenylethyl group and β-phenylethyl group.

Examples of halogenated hydrocarbon groups are chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 5,5,5,4,4,3,3-heptafluoro group. Examples thereof include a pentyl group, a chlorophenyl group, a dichlorophenyl group and a trifluorotolyl group.

Examples of the mercaptoalkyl group include 2-
Examples thereof include a mercaptoethyl group and a 3-mercaptopropyl group.

Examples of the cyanoalkyl group include a 2-cyanoethyl group and a 3-cyanopropyl group.

An example of an acyloxyalkyl group is 3
Examples thereof include an acryloxypropyl group and a 3-methacryloxypropyl group.

Examples of the aminoalkyl group include 3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group and N- (2-aminoethyl) -3-amino- group.
(2-methyl) -propyl group and the like can be mentioned.

Examples of the aminoaryl group include aminophenyl group and the like.

Examples of hydroxyalkyl groups include hydroxypropyl groups and the like.

Examples of glycidoxyalkyl groups include 3
-Glycidoxypropyl group and the like can be mentioned.

Of these, methyl group, ethyl group, n-
From the viewpoint of performance and economy, it is preferable to use an organic group selected from the group consisting of a propyl group, an isopropyl group, an isooctyl group, a vinyl group and a phenyl group.

The mixing ratio of the organopolysiloxane (B) is 0.1 to 30 with respect to 100 parts by weight of the resin component (A).
The range is from 0.5 to 20 parts by weight, preferably from 1 to 15 parts by weight. If the amount is less than 0.1 parts by weight, the flame retardance is not sufficiently improved, which is not preferable. On the other hand, if it exceeds 30 parts by weight, mechanical properties such as impact resistance are deteriorated, which is not preferable. The organopolysiloxane (B) may be used alone or in combination of two or more kinds.

The method for producing the organopolysiloxane (B) is not particularly limited, and known methods can be used. For example,
It can be obtained by hydrolytic polycondensation of organochlorosilane, organoalkoxysilane or the like in the presence of excess water and a catalyst such as acid or base. At that time, the content of the M unit, D unit, T unit, and Q unit is controlled by adjusting the structures of the organochlorosilane, organoalkoxysilane, and the like to be used and the compounding amounts thereof, and the organopolypolysiloxane having a desired branched structure is controlled. Siloxane (B) can be obtained. Further, the molecular weight of the organopolysiloxane (B) can be adjusted by adjusting the type and amount of the catalyst used, the amount of water, the temperature and time of the hydrolysis polycondensation reaction, the amount of M unit introduced, and the like.

The branched structure of the organopolysiloxane (B) is not particularly limited as long as the content of each of the M unit, D unit, T unit and Q unit is within the above range, and various types can be used. Examples thereof include a linear structure composed of D units, a cyclic structure, and a branched structure composed of each combination of T, DT, DQ, TQ, and DTQ. Further, as a structure in which an end group composed of M units is further introduced, a linear structure composed of a combination of MD, and MT, MQ, MDT, MDQ,
A branched structure composed of each combination of MTQ and MDTQ can be mentioned.

Organopolysiloxane (B) synthesized by a combination selected from D unit, T unit and Q unit
Contains a hydroxyl group and / or an alkoxy group directly bonded to a silicon atom as an end group, depending on the production method. The alkyl group in the alkoxy group depends on the starting material for producing the organopolysiloxane (B) and the solvent used for the production, and is usually a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. is there.

Since these terminal groups, especially the hydroxyl groups, have high reactivity, when they are present in a large amount in the organopolysiloxane, they are hydrolyzed to form crosslinks, which deteriorates the moldability of the resin composition. When compounded in the components, it may react with the aromatic polycarbonate at a high temperature, and a side reaction such as a decrease in the molecular weight of the aromatic carbonate may occur, which is not preferable in some cases. In such a case, by treating the terminal hydroxyl group with a silylating agent described later, it can be converted into M units and the organopolysiloxane (B) can be stabilized.

The introduction of M units into the skeleton of the organopolysiloxane (B) can be carried out not only in such a silylation treatment after the hydrolytic condensation polymerization, but also at the time of the hydrolytic condensation polymerization.

Specific examples of the organochlorosilanes and organoalkoxysilanes used in the production of the organopolysiloxane (B) and other raw materials include the following.

As the raw material of the D unit, dimethyldichlorosilane, diethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, Methyl vinyl dimethoxy silane,
Examples thereof include methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane.

As a raw material for the D unit other than the above, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,
3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,
3,5,7-tetraphenylcyclotetrasiloxane,
Hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane and the like can be mentioned.

As the raw material of the T unit, methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, n-propyltrichlorosilane, isopropyltrichlorosilane, phenyltrichlorosilane, isooctyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane. , Ethyltrimethoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, iso Examples include octyltrimethoxysilane and isooctyltriethoxysilane.

Examples of the raw material for the Q unit include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and the like.

Examples of silylating agents for introducing M units include chlorosilanes such as trimethylchlorosilane, triethylchlorosilane, dimethylphenylchlorosilane, diphenylmethylchlorosilane, triphenylchlorosilane, dimethylvinylchlorosilane, hexamethyldisilazane, 1, Examples thereof include disilazane such as 3-divinyltetramethyldisilazane.

Examples of M unit raw materials other than the silylating agent include hexamethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 1,3-divinyltetramethyldisiloxane.

The content of the terminal hydroxyl group in the organopolysiloxane (B) is preferably 5% by weight or less, more preferably 1% by weight or less. The content of the terminal alkoxy group in the organopolysiloxane (B) is preferably 10% by weight or less, more preferably 5% by weight or less.

The content of the hydroxyl group can be determined by, for example, a method of quantifying the amount of gas generated when the reaction is performed with an organometallic compound such as alkyllithium or alkylmagnesium halide (Grignard reagent) in an anhydrous solvent. The content of the alkoxy group can be calculated from the signal area ratio of the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum, for example, in combination with an appropriate internal standard substance.

The weight average molecular weight of the organopolysiloxane (B) is preferably 500 to 100,000,
0-40,000 are more preferable, 1,000-10,
000 is more preferable.

When the weight average molecular weight is lower than 500, the volatility of the organopolysiloxane (B) is too high, or the compatibility with the resin component (A) is too high, and the resin component (A) is plasticized. As a result, the flame retardancy of the resin composition decreases, which is not preferable. Conversely, the weight average molecular weight is 100,0
When it exceeds 00, the dispersibility of the organopolysiloxane (B) in the resin component (A) decreases, the flame retardancy of the resin composition becomes insufficient, and the mechanical properties of the resin composition deteriorate. It is not preferable.

The preferred structure of the organopolysiloxane (B) is a straight chain structure composed of a combination of MD, DT and M.
It is a branched structure composed of each combination of DT, MQ, MDQ, MTQ, and MDTQ.

In particular, an organopolysiloxane (so-called MQ resin) mainly composed of an MQ structure and obtained by introducing D units and / or T units as desired is a particularly preferable structure. Such an organopolysiloxane is
For example, Japanese Patent Publication No. 8-22921 (US Pat. No. 5,5,5)
Corresponding to Japanese Patent No. 48,053) and Japanese Patent No. 294170.
Good production can be achieved by the method disclosed in Japanese Patent Publication No. 1 (corresponding to US Pat. No. 5,786,413).

The preferred structure of the organopolysiloxane (B) is shown by composition. When the organopolysiloxane (B) mainly has a DT structure, M unit is 0 to 30 mol%, D unit and T unit are contained. The total amount is in the range of 70 to 100 mol%, more preferably 0 to 30 mol% of the M unit, 70 to 100 mol% of the total of the D unit and the T unit, and the mol of the D unit and the T unit. Ratio is 10/90 to 90 /
The range is 10. When the organopolysiloxane (B) mainly has an MQ structure, the M unit is 10
˜50 mol%, Q unit 15 to 60 mol%, D unit and T
The total amount of units is in the range of 0 to 70 mol, more preferably 10 to 50 mol% of M units and 15 to 10 of Q units.
60 mol% and the total of D units and T units is in the range of 5 to 70 mol.

The inorganic alkali metal salt and / or the inorganic alkaline earth metal salt (hereinafter referred to as "inorganic metal salt") used as the component (C) of the present invention is a component which is a feature of the present invention. It is a component that plays an important role in imparting flame retardancy to the resin component (A) through a synergistic effect with the polysiloxane (B).

The inorganic alkali metal salt and the inorganic alkaline earth metal salt used in the component (C) of the present invention are formed between the inorganic acid and the alkali metal element and the inorganic acid and the alkaline earth metal element, respectively. is there.

The alkali metal element used in the inorganic metal salt (C) is lithium, sodium, potassium, rubidium or cesium, preferably sodium or potassium.

The alkaline earth metal element used in the inorganic metal salt (C) is beryllium, magnesium, calcium, strontium or barium, preferably magnesium or calcium.

Examples of the inorganic acid used for producing the inorganic metal salt (C) include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, thiosulfuric acid, pyrosulfurous acid and dithionous acid. , Nitric acid, nitrous acid, phosphoric acid, pyrophosphoric acid, boric acid, hexafluoroaluminic acid, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorophosphoric acid,
Examples thereof include tetrafluoroboric acid.

Preferred examples of the inorganic metal salt (C) are alkali metal halide salts formed between hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide and an alkali metal element or an alkaline earth metal element. , An alkaline earth metal halide salt.

Specific examples of the alkali metal halide and the alkaline earth metal halide include LiF and
LiCl, LiBr, LiI, NaF, NaCl, Na
Br, NaI, KF, KCl, KBr, KI, Mg
F ₂ , MgCl ₂ , MgBr ₂ , MgI ₂ , CaF ₂ , Ca
Examples include Cl ₂ , CaBr ₂ , and CaI ₂ . Of these, it is particularly preferable to use NaCl, NaBr, KCl or KBr.

Specific examples of inorganic metal salts (C) other than the above
As Na₂SO_Four, K₂SO_Four, MgSO_Four, CaS
O_Four, Na₂SO₃, K₂SO₃, MgSO₃, CaSO₃,
Na₂S₂O₃, K₂S₂O₃, MgS₂O₃, CaS₂O₃, N
a₂S₂O_Five, K₂S₂O_Five, MgS₂O_Five, CaS₂O_Five, Na
₂S₂O_Four, K₂S₂O_Four, MgS₂O_Four, CaS₂O_Four, NaN
O₃, KNO₃, Mg (NO₃)₂, Ca (NO₃)₂, Na
NO₂, KNO₂, Mg (NO₂)₂, Ca (NO₂)₂, N
a₃PO_Four, K₃PO_Four, Mg₃(PO_Four)₂, Ca₃(P
O_Four)₂, Na_FourP₂O₇, K_FourP₂O₇, Mg₂P₂O₇, Ca₂
P₂O₇, Na₂B_FourO ₇, K₂B_FourO₇, MgB_FourO₇, CaB
_FourO₇, Na₃AlF₆, K₃AlF₆, Mg₃(Al
F₆)₂, Ca₃(AlF₆)₂, Na₂SiF₆, K₂SiF
₆, MgSiF₆, CaSiF₆, Na₂TiF₆, K₂Ti
F₆, MgTiF₆, CaTiF₆, NaPF₆, KP
F₆, Mg (PF₆)₂, Ca (PF₆)₂, NaBF_Four, K
BF_Four, Mg (BF_Four)₂, Ca (BF_Four)₂Is mentioned
It

The blending ratio of the inorganic metal salt (C) is 0.0005 to 5 parts by weight based on 100 parts by weight of the resin component (A),
Preferably 0.001 to 2 parts by weight, more preferably 0.1.
It is in the range of 005 to 1 part by weight. If it is less than 0.0005 parts by weight, the flame retardance is not sufficiently improved, which is not preferable. On the other hand, if the amount exceeds 5 parts by weight, the thermal stability and hydrolysis resistance of the aromatic polycarbonate deteriorate, and mechanical properties such as impact resistance are impaired, which is not preferable. Inorganic metal salt (C)
The inorganic alkali metal salt or the inorganic alkaline earth metal salt may be used alone or in any combination of two or more kinds.

In the present invention, it is essential to use the organopolysiloxane (B) and the inorganic metal salt (C) together. Although the flame retardancy improving effect is insufficient only by adding the organopolysiloxane (B) to the resin component (A),
Furthermore, flame retardancy can be greatly improved by adding an inorganic metal salt (C). Further, even if only the inorganic metal salt (C) is added to the resin component (A), the flame retardancy improving effect is hardly obtained.

The feature of the present invention is that a small amount of inorganic metal salt (C) is used in addition to the organopolysiloxane (B), and the synergistic effect of both components results in a resin component containing a flammable styrene resin. The point is that the flame retardancy of (A) can be improved. On the other hand, when an organic sulfonic acid metal salt widely known as a flame retardant for aromatic polycarbonate is used, a synergistic effect with such an organopolysiloxane cannot be obtained or a flame retardant effect can be obtained. It has been found that a large amount of organic sulfonic acid metal salt needs to be added.

In the present invention, the reason why the excellent flame retardancy-improving effect is exhibited by using the organopolysiloxane (B) and the inorganic metal salt (C) together as described above is not clear at present, but Is speculated as.

When a carbonized layer (char) is formed from a resin component, especially an aromatic polycarbonate during combustion, when organopolysiloxane which is a flame retardant coexists, SiO ₂ derived from the organopolysiloxane is integrated with the carbonized layer. Therefore, it is considered that a barrier layer having high flame retardancy is formed. When a flammable resin such as a styrene resin coexists in the resin component, it is considered necessary to form the barrier layer more quickly and efficiently in order to prevent the decomposition thereof. It is presumed that the inorganic metal salt (C) has a function of efficiently accelerating the formation of the barrier layer from the organopolysiloxane (B) and the aromatic polycarbonate.

As the method for producing the flame-retardant resin composition of the present invention, known methods can be used and are not particularly limited.

For example, the resin component (A), the organopolysiloxane (B), and the inorganic metal salt (C) are premixed and then melt-mixed at a temperature equal to or higher than the softening point of the resin component (A); A method in which A) and the inorganic metal salt (C) are pre-mixed and further made into a molten state, and then the organopolysiloxane (B) is mixed; organopolysiloxane (B)
And the inorganic metal salt (C) are premixed and then mixed with the resin component (A) in a molten state; the organopolysiloxane (B) and the inorganic metal salt (C) are partially mixed with the resin component (A) in advance. A method of melt-mixing to form a masterbatch, which is added to the rest of the resin component (A), etc. may be mentioned.

As the premixing method, a dry blending method; a method using a Henschel mixer, a super mixer, a tumble mixer, a ribbon blender, or the like; (A)
A part of or all of components (C) to (C) are dissolved in water or a solvent, mixed, and then dried, followed by a wet method.

As a method of melt mixing, a method using a single screw extruder, a twin screw extruder, a Banbury mixer, a Brabender, etc. can be used.

As one of the particularly preferable methods for producing the flame-retardant resin composition of the present invention, the inorganic metal salt (C) is preliminarily and uniformly mixed with the organopolysiloxane (B),
A method of producing an organopolysiloxane containing an inorganic metal salt and then mixing this with the resin component (A) can be mentioned. By using this production method, the synergistic effect of the organopolysiloxane (B) and the inorganic metal salt (C) is easily exhibited, and a higher flame retardancy improving effect is obtained.

As a method for uniformly mixing the inorganic metal salt (C) with the organopolysiloxane (B), the organopolysiloxane (B) is heated to a temperature above its softening point and then the inorganic metal salt (C) is added. And melt-mixing; organopolysiloxane (B) and inorganic metal salt (C) dissolved in the same or different solvents, respectively, and then mixed and dried; organopolysiloxane (B) The acid / base catalyst used in the production of the above-mentioned method, and the salt formed from the acid / base used in the further neutralization thereof are not removed but remain in the organopolysiloxane. Examples include a method of collecting and using siloxane. In particular, the method of using a salt produced when producing the organopolysiloxane (B) is preferable because the inorganic metal salt can be uniformly dispersed at low cost.

For example, in the method for producing the MQ resin disclosed in Japanese Patent Publication No. 8-22921 mentioned above, the alkoxysilanes as the raw material are subjected to a polycondensation step (first step) using an acid catalyst and a base catalyst. MQ resin is produced through a second step of a polycondensation step (second step) in which the compound is used, and a third step of neutralizing the base catalyst with an acid. Here, for example, by using HCl as an acid in the first step and the third step and NaOH as a base in the second step, an MQ resin containing NaCl can be produced. The MQ resin thus produced is preferably used in the present invention as the organopolysiloxane (B) containing the inorganic metal salt (C).

The content of the inorganic metal salt (C) contained in the flame-retardant resin composition of the present invention and the organopolysiloxane (B) can be quantified by a known method. For example, a resin composition or an organopolysiloxane containing an inorganic metal salt (C) is dissolved in a solvent and then extracted with water, or decomposed at a high temperature in the presence or absence of an acid or a peroxide. After that, the element to be quantified is recovered by a method such as extraction in a solvent, and coulometric titration method, atomic absorption method, emission analysis method,
It can be quantified by a method such as an ion chromatography method and a fluorescent X-ray method. In addition, a resin composition or an organopolysiloxane containing an inorganic metal salt (C) is analyzed by a direct fluorescent X-ray method, and the FP method (Fundamenta) is analyzed.
(1 Parameter method), a calibration curve method, or the like.

In the present invention, a flame retardant other than the organopolysiloxane (B) and the inorganic alkali metal salt and / or the inorganic alkaline earth metal salt (C) is used in combination in order to impart higher flame retardancy. Is also possible. For example, a) phosphate ester compounds, b) inorganic phosphorus compounds such as red phosphorus and ammonium polyphosphate, c) halogenated organic compounds, d) nitrogen-containing organic compounds such as melamine, melamine cyanurate, melam, melem, and melon. Compound,
e) an inorganic metal salt other than alkali and alkaline earth metals such as zinc borate and zinc stannate, f) antimony oxide,
Metal oxides such as molybdenum oxide, titanium oxide, zirconium oxide, zinc oxide, etc. g) Cyclic or linear form such as polyphenoxyphosphazene, polytolyloxyphosphazene, polymethoxyphosphazene, polyphenoxymethoxyphosphazene, polyphenoxytolyloxyphosphazene A phosphazene polymer or oligomer,
h) phenol, cresol, t-butylphenol,
One or more compounds selected from phenolic resins such as phenylphenol and formaldehyde and phenolic resins such as novolac resins and resole resins are used. Among these, a) phosphoric acid ester compounds, which are relatively less toxic and less deteriorated in physical properties, are preferable.

Examples of a) phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylyl phosphate, dimethyl ethyl phosphate. Examples thereof include phosphoric acid esters such as methyl dibutyl phosphate, ethyl dipropyl phosphate, and hydroxyphenyl diphenyl phosphate, compounds in which various substituents are introduced, and condensed phosphoric acid ester compounds represented by the following formula (10). .

[0114]

[Chemical 14]

(In the formula, n is an integer of 1 to 10, and Ar is
¹ , Ar ² , Ar ⁴ and Ar ⁵ are each independently an aromatic group selected from a phenyl group which is unsubstituted or substituted with at least one hydrocarbon group having 1 to 10 carbon atoms, and Ar ³ has 6 carbon atoms. To 20 divalent aromatic groups. )

Examples of the condensed phosphoric acid ester compounds include bisphenol A tetraphenyl diphosphate, bisphenol A tetratolyl diphosphate, bisphenol A tetraxylyl diphosphate, bisphenol A di (phenylxylyl phosphate), resorcinol tetraphenyl diphosphate, Resorcinol tetraxylyl diphosphate is preferably used.

Further, in the present invention, a fluoroolefin resin can be used in order to further reduce the dropping of combustion particles during combustion. The fluoroolefin resin used here is a homo- or copolymer containing a fluoroethylene structure, for example, a difluoroethylene polymer,
Examples thereof include trifluoroethylene polymers, tetrafluoroethylene polymers, tetrafluoroethylene-hexafluoropropylene copolymers, copolymers of tetrafluoroethylene and fluorine-free ethylene-based monomers. Polytetrafluoroethylene (PTFE) is particularly preferably used, and its molecular weight and morphology are not particularly limited, but it is preferable to disperse it in the form of fibrils having a diameter of 0.5 μm or less in the composition. The amount of the fluoroolefin resin added is 0.01 to 3 with respect to 100 parts by weight of the resin component (A).
The range is parts by weight. If the amount used is less than this range, the anti-dripping effect is not sufficient, and if the amount used is more than this range, fluidity and flame retardancy are reduced, which is not preferable.

The flame-retardant resin composition of the present invention has a moldability,
For the purpose of improving impact resistance, rigidity, weather resistance, appearance and the like, various additives commonly used in thermoplastic resins can be added. Examples of additives include heat stabilizers, antioxidants, ultraviolet absorbers, weathering agents, antibacterial agents, compatibilizers, colorants (dye, pigment), release agents, lubricants, antistatic agents, plasticizers,
Other resins, polymers such as rubber, fillers, etc. may be mentioned.
The amount added is not particularly limited as long as the characteristics of the flame-retardant resin composition of the present invention are maintained.

The flame-retardant resin composition of the present invention is used in copying machines, fax machines, televisions, radios, tape recorders, VCRs, personal computers, printers, telephones, information terminals,
Mobile phones, refrigerators, microwave ovens and other office automation equipment, information /
It is suitable for use in housings of communication equipments, electric / electronic equipments, home appliances, or various parts thereof, and also automobile parts.

[0120]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The following components were used in Examples and Comparative Examples. (A-1) Aromatic polycarbonate PC: Mitsubishi Engineering Plastics Co., Ltd.
Bisphenol A Polycarbonate Iupilon S30
00 Viscosity average molecular weight 20,000 (A-2) Styrenic resin AS: Asahi Kasei Co., Ltd. acrylonitrile-styrene copolymer Styrac AS T8801 ABS: Mitsubishi Rayon Co., Ltd. powdery acrylonitrile-butadiene-styrene copolymer RV

(B) Organopolysiloxane S-1 and S-8 to S-15: JP-B-8-22921
Acid catalyst (HCl) and base catalyst (NaOH) from the corresponding ethoxysilanes according to the method disclosed in the publication.
Was synthesized using. S-2 and S-3: Synthesized by hydrolytic polycondensation of the corresponding chlorosilane. S-4: T unit 1 obtained by hydrolytic condensation polymerization of chlorosilane
00% of organopolysiloxane was synthesized by further reacting with hexamethyldisilazane to introduce M units. S-5: PMM0021 manufactured by Gelest was used. S-6: Referring to the method disclosed in Japanese Examined Patent Publication No. 8-22921, acid catalyst (HC
1) and a base catalyst (NaOH). S-7: Only the acid catalyst (HCl) was used, and the base catalyst (Na
It was synthesized by the same method as S-6 except that OH) was not used. S-16: Shin-Etsu Chemical Co., Ltd. LS-8730 was used.

The molar ratio of M units, D units, T units and Q units constituting the organopolysiloxane (B), and the structure and composition ratio (molar ratio) of the organic group R are as follows: proton and silicon 29 nuclear magnetic resonance ( ¹ H- and ²⁹ Si-NMR) spectroscopic analysis. ¹ H- and ²⁹ Si-NMR spectra were measured using Avance D with heavy benzene as a solvent.
It was obtained using a PX400 type or DPX300 type nuclear magnetic resonance apparatus (both manufactured by Bruker, Germany), or using deuterated chloroform as a solvent, using a JNM-α400 type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.).

The weight average molecular weight of the organopolysiloxane (B) was determined as a polystyrene equivalent weight average molecular weight by gel permeation chromatography (GPC). The GPC measurement is performed under the following condition 1 or condition 2.
Went in either.

<Condition 1> Apparatus: 307 type chromatographic column manufactured by Abimed, Germany: Pl gel Mixed-C and 100A
(Both are manufactured by Hewlett-Packard, USA) used in series Eluent: Toluene or tetrahydrofuran Detection: Model 8120 differential refractive index detector manufactured by Bischoff, Germany

<Condition 2> Equipment: Shimadzu LC-10 type chromatographic column: Shodex K-806M, K-804 and K-802.5 (all manufactured by Showa Denko) are used in series. Eluent: Chloroform detection: Shimadzu SPD-10A type UV absorption detector

The organopolysiloxane (B) has a hydroxyl group (silanol group) directly bonded to a silicon atom and an ethoxy group as terminal groups. The content was determined as follows.

(1) Silanol Group Content (% by Weight) The polyorganosiloxane (B) was reacted with methylmagnesium iodide (MeMgI, Grignard reagent) in anhydrous xylene, and the content was determined from the volume of methane generated.

(2) Content of terminal ethoxy group (% by weight) It was determined from the ratio of signal areas in ¹ H-NMR spectrum using tetrachloroethane or dichloromethane as an internal standard. ¹ H-NMR spectrum was obtained under the same conditions as above.

The content of the inorganic metal salt in the organopolysiloxane (B) was determined by using a fluorescent X-ray analyzer or a flameless atomic absorption spectrophotometer. Fluorescent X-ray analysis was performed using a Rig3000 fluorescent X-ray analyzer manufactured by Rigaku Co., Ltd.
It was carried out by the undamental Parameter method. In addition, flameless atomic absorption spectrometry was performed using Hitachi's Z-8270 after pretreatment of organopolysiloxane with sulfuric acid and hydrofluoric acid. No inorganic metal salts were detected from the organopolysiloxanes S-1 to S-5, S-7 and S-16, but from the organopolysiloxanes other than these, Na derived from the catalyst during synthesis was used.
Cl was detected. The characteristics of the organopolysiloxane (B) obtained by the above method are shown in Table 1.

In the comparative examples, the following commercially available metal salts of organic sulfonic acids were used. F114P: Potassium perfluorobutane sulfonate Megafac F114 manufactured by Dainippon Ink and Chemicals, Inc.
PKSS: UCB Japan diphenyl sulfone-3-
Potassium sulfonate

[0132]

[Examples 1 to 6] With the composition shown in Table 2, first, a methanol solution or an aqueous solution of an inorganic metal salt (C) was mixed with an aromatic polycarbonate, and the mixture was dried at 120 ° C for 4 hours to prepare the aromatic polycarbonate and the inorganic metal. A salt premix was obtained. This pre-mixture, the styrene resin and the organopolysiloxane (B) were placed in a polyethylene bag with the composition shown in Table 2 and further pre-mixed by manual mixing to obtain an extruder (KZW manufactured by Techno Bell Co., Ltd., Japan).
15-45 MG) and melt-kneaded at 250 ° C.
The obtained resin composition (pellet) is 250 ° C. in a small injection molding machine (MJEC10) manufactured by Modern Machinery Co., Ltd. of Japan.
Was molded into a test piece having a thickness of 3.18 mm.

A vertical burning test based on UL-94 was carried out using the prepared test piece to evaluate the self-extinguishing property of the resin composition. The results are shown in Table 2.

As is clear from Table 2, the resin composition of the present invention does not cause the dropping of combustion particles and exhibits excellent flame retardancy (self-extinguishing property).

[0135]

Comparative Example 1 The same operations as in Examples 1 to 6 were carried out except that the test piece was prepared using only the aromatic polycarbonate and the styrene resin without using the organopolysiloxane and the inorganic metal salt. The results are shown in Table 2. As is clear from Table 2, combustion particles were dropped and the combustion time was long.

[0136]

Comparative Example 2 The same operations as in Examples 1 to 6 were carried out except that a test piece was prepared using a resin mixture containing an aromatic polycarbonate, a styrene resin and an organopolysiloxane without using an inorganic metal salt. The results are shown in Table 2. As is clear from Table 2, combustion particles were dropped and the combustion time was long. From this result, it is understood that the effect of improving the flame retardancy is insufficient only with the organopolysiloxane.

[0137]

[Comparative Examples 3 and 4] Specimens were prepared by using a resin mixture containing an aromatic polycarbonate, a styrene resin and a metal salt of an organic sulfonic acid (F114P) or an inorganic metal salt (NaCl) without using organopolysiloxane. The same operation as in Examples 1 to 6 was performed. The results are shown in Table 2. As is clear from Table 2, combustion particles were dropped and the combustion time was long. From this result, it can be seen that the salt alone has no effect of improving the flame retardancy.

[0138]

[Comparative Examples 5 to 8] The same operations as in Examples 1 to 6 were performed, except that a test piece was prepared using an organic sulfonic acid metal salt (F114P, KSS) instead of the inorganic metal salt. The results are shown in Table 2. As is clear from Table 2, the organic sulfonic acid metal salt is not effective in improving the flame retardancy, and the burning time is longer than that of Comparative Example 1.

From the results of Examples 1 to 6 and Comparative Examples 1 to 8 described above, it is possible to obtain a large flame retardancy-improving effect only when the organopolysiloxane and the inorganic metal salt are used in combination. It can be seen that the effect is exhibited even in a small amount, whereas the conventionally used organic sulfonic acid metal salt does not exhibit the effect.

[0140]

Examples 7 to 11 Organopolysiloxanes S-2 to S having various structures as the organopolysiloxane (B)
-5 was used. Examples 1 to 6 according to the composition shown in Table 3
Test pieces were prepared and self-extinguishing property was evaluated by the same operation as described in 1. In Examples 9 and 11, the obtained resin composition (pellet) was used for compression molding using a compression molding machine.
A test piece having a thickness of 3.18 mm was prepared by compression molding at 0 ° C. The results are shown in Table 3. As is clear from Table 3, regardless of the structure of the organopolysiloxane,
All exhibited excellent flame retardancy improving effects.

[0141]

Comparative Examples 9 to 12 The same organopolysiloxanes S-2 to S-5 as those used in Examples 7 to 11 were used, and the same operation was repeated without using the inorganic metal salt. The results are shown in Table 3.
Shown in. As is clear from Table 3, when the inorganic metal salt is not used in combination, the dropping of the combustion particles cannot be prevented and the combustion time becomes long.

[0142]

Examples 12 to 16 Organopolysiloxanes S-6 and S-containing NaCl derived from the catalyst used in the synthesis
8, S-10, S-12 and S-14 were used. Aromatic polycarbonate, styrenic resin, and organopolysiloxane having the composition shown in Table 4 were premixed, and Example 1 was used.
The test pieces were prepared and self-extinguishing property was evaluated by the same operation as the method described in 1-6. The inorganic metal salt is not added from the outside, and NaC which is previously contained in the organopolysiloxane.
Only 1 was used. The results are shown in Table 4. As is clear from Table 4, an excellent flame retardancy-improving effect was observed even though no inorganic metal salt was added from the outside.

[0143]

Comparative Examples 13 to 16 Organopolysiloxanes S-6, S-8, S-10 and S used in Examples 12 to 15 above.
Organopolysiloxane S-7, S- having the same or almost the same structure as -12 and a low content of inorganic metal salt
9, S-11 and S-13 were used. Aromatic polycarbonate, styrenic resin and organopolysiloxane having the composition shown in Table 4 were premixed, and a test piece was prepared and self-extinguishing property was evaluated by the same operation as the method described in Examples 1 to 6. . The inorganic metal salt was not added from the outside, and only NaCl which was previously contained in the organopolysiloxane was used. The results are shown in Table 4. As is clear from Table 4, the content of the inorganic metal salt in the resin composition is 0.0005% by weight.
Since it is less than the above range, dropping of combustion particles occurs and combustion time becomes extremely long.

[0144]

Comparative Examples 17 and 18 In Comparative Example 17, a high molecular weight MQ resin S-15 containing 65 mol% of Q unit was used as the organopolysiloxane (B). Aromatic polycarbonate, styrenic resin and organopolysiloxane having the composition shown in Table 4 were premixed, and a test piece was prepared and self-extinguishing property was evaluated by the same operation as the method described in Examples 1 to 6. . S-15 contained NaCl derived from the catalyst used at the time of synthesis, and was evaluated without adding any other inorganic metal salt from the outside.

In Comparative Example 18, a low molecular weight silicone compound S-16 containing 75 mol% of M unit was used as the organopolysiloxane (B). Since S-16 does not contain an inorganic metal salt, NaCl was added in the same manner as in Examples 1 to 6 to prepare a test piece and evaluate its self-extinguishing property. The results are shown in Table 4.

As is clear from Table 4, burning particles were dropped and the burning time was long. From these results, it is understood that the organopolysiloxane having a high content of Q units or M units is inferior in the flame retardancy improving effect even when the inorganic metal salt is used in combination.

[0147]

[Table 1]

[0148]

[Table 2]

[0149]

[Table 3]

[0150]

[Table 4]

[0151]

INDUSTRIAL APPLICABILITY The resin composition of the present invention uses highly safe organopolysiloxane and exhibits good flame retardancy and moldability. Therefore, the resin composition of the present invention is
It is a material that can sufficiently cope with the increase in size and thickness of equipment A, information and communication equipment, electric / electronic equipment, home appliances, automobile parts, etc., and its application fields are expected to expand.

Continued front page    (72) Inventor Koji Oda             Asahi Kasei Co., Ltd. 3-13-1, Shiodori, Kurashiki City, Okayama Prefecture             Inside the company (72) Inventor Tsunetaro Kuwata             Asahi Kasei Co., Ltd. 3-13-1, Shiodori, Kurashiki City, Okayama Prefecture             Inside the company F term (reference) 4J002 BC022 BC052 BN062 BN152                       BN162 CG011 CG021 CP053                       CP083 CP093 CP103 DD026                       DD056 DD066 DD076 DD086                       FD133 FD136 GQ00

Claims (4)

[Claims] 1. 100 parts by weight of a resin component (A) comprising 50 to 95% by weight of an aromatic polycarbonate and 50 to 5% by weight of a styrene resin, and an organopolysiloxane (B).
0.1 to 30 parts by weight, and an inorganic alkali metal salt and / or an inorganic alkaline earth metal salt (C) 0.0005
A flame-retardant polycarbonate resin composition containing 5 parts by weight, wherein the organopolysiloxane (B) is represented by the following formula (1): (In the formula, each R is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a mercaptoalkyl group having 1 to 20 carbon atoms, and a carbon number. Two
˜20 cyanoalkyl group, C 2-20 acyloxyalkyl group, C 1-20 aminoalkyl group,
It is a monovalent organic group selected from the group consisting of an aminoaryl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and a glycidoxyalkyl group having 4 to 20 carbon atoms. ) A monofunctional siloxane unit (M unit) represented by the following formula (2): (In the formula, R is the same as that defined in the above formula (1).) A difunctional repeating siloxane unit (D
Unit); the following formula (3): (In the formula, R is the same as that defined in the above formula (1).) The trifunctional repeating siloxane unit (T
Unit); the following formula (4): A tetrafunctional repeating siloxane unit (Q unit) represented by
The M unit in the organopolysiloxane (B), based on the total molar amount of the M unit, the D unit, the T unit, and the Q unit in the organopolysiloxane (B),
The content of the D unit, the T unit, and the Q unit is 0 to 7 respectively.
0 mol%, 0-100 mol%, 0-100 mol%, 0
The composition is 63 mol%. 2. An organic group R in the formulas (1), (2) and (3)
Is independently selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, isooctyl group, vinyl group and phenyl group. 3. The inorganic alkali metal salt and / or inorganic alkaline earth metal salt (C) is at least one selected from the group consisting of alkali metal halides and alkaline earth metal salts. Claim 1 characterized by
The composition according to 1 to 2. 4. The composition according to claim 1, wherein at least one selected from the group consisting of NaCl, KCl, NaBr and KBr is used as the component (C).